The invention relates to starch-graft copolymer compositions which absorb and retain under pressure large quantities of aqueous fluids and to their method of preparation. The invention further relates to various compositions and articles of manufacture which utilize the instant composition.
Crosslinked polymeric substances which possess the ability to absorb large quantities of fluids are known in the prior art. For example, U.S. Pat. No. 3,669,103 discloses that a variety of monomers may be polymerized to give copolymers and terpolymers which must be crosslinked in manners known in the polymer arts. One such copolymer contains carboxamide and carboxylate groups and is crosslinked by including a difunctional monomer such as N,N-methylenebisacrylamide into the polymerization solution. The crosslinking reaction is of critical importance. When the copolymers and terpolymers are not crosslinked, they are water soluble and have limited utility as absorbents.
U.S. Pat. No. 3,670,731 discloses the utility of particulate, water-insoluble, crosslinked polymeric compositions as absorbents in fabricated articles such as diapers, sanitary napkins, and the like.
It is an object of this invention to provide polymeric absorbent compositions which have the preparative ease and economic advantages inherent in starch graft copolymers and which will absorb aqueous fluids in quantities many times their own weight.
It is a further object of the invention to provide polymeric absorbent compositions which have not been subjected to normally used crosslinking compositions or procedures and yet are water-insoluble solids.
In accordance with the objects of the invention, we prepared aqueous fluid-absorbing compositions comprising water-insoluble alkali salts of saponified gelatinized-starch-polyacrylonitrile graft polymers containing gelatinized starch (GS) and saponified polyacrylonitrile (HPAN) in molar ratios of from about 1:1.5 to 1:9 GS:HPAN. The water-insoluble alkali salts of saponified gelatinized-starch-polyacrylonitrile graft polymers are further characterized as water-insoluble solids capable of absorbing in excess of 300 parts of water by weight per part of the water-insoluble solids.
Compositions comprising water-insoluble organic amine salts of the compositions described above were found to absorb aqueous fluids which contain organic components in major porportions.
Also in accordance with the objects of the invention, we discovered a method of preparing water-insoluble aqueous fluid-absorbing compositions comprising the following steps:
A. saponifying a gelatinized starch-polyacrylonitrile graft polymer (GS-PAN) in an aqueous slurry with an alkali in amounts such that the molar ratio of alkali to the acrylonitrile repeating unit of said GS-PAN is from about 0.1:1 to 7:1 to form a water-soluble saponified GS-PAN (water-soluble GS-HPAN; and PA1 b. optionally adjusting the pH of said water-soluble GS-HPAN to about 3 followed by isolating the resulting water-insoluble acid form of GS-HPAN, and readjusting the pH of said water-insoluble acid form of GS-HPAN to from about 4 to 12 to reform said water-soluble GS-HPAN; and PA1 c. drying said water-soluble GS-HPAN to a moisture level of from about 1 to 15% water by weight.
Incorporation of the instant compositions in disposable soft goods such as diapers, hospital bed pads, surgical pads and sheets, catamenial devices, and the like would greatly increase the fluid-absorbing capacity of the articles. Such increased absorbency of the disposable soft goods is important from both an economic and an ecological standpoint, since the higher absorbency permits the use of a smaller quantity of material to be disposed of by incineration or by discharge into sewage systems. The use of smaller quantities of GS-HPAN also decreases the amount of the synthetic polymers used in the application of the invention. Acrylonitrile is a petrochemical, and its decreased consumption increases the amount of petroleum that can be diverted to more urgently needed products. The instant compositions are also useful in agricultural applications for increasing water-holding capacity of soils which promotes more efficient germination of seeds and plant growth.
When the instant compositions were applied as coatings onto substrates such as seeds, clay, starch, fibers, paper, or the like, a large increase in the water-holding capacity of the substrate was realized.
The organic amine salts of the invention, which absorb large amounts of aqueous-organic fluids, are useful in the formulation of jellied fuels, paint removers, and other formulations where it is desirable to have an organic solvent, containing a minimum amount of water, in an essentially solid form.